Production of diamino-anthraquinonyloxdiazoles



PRODUCTION OF DIAMINO-ANTHRAQUINONYL- OXDIAZOLES Heinz-Werner Schwechten, Leverlrusen-Bayerwerk, Germany, assignor to Farbenfabriken Bayer Aktiengesellsclraft, Leverkusen, Germany, a corporation of Germany No Drawing. Application April 30, 1953, Serial No. 352,299

Claims priority, application Germany May 7, 1952 5 Claims. (Cl. 260-3075) The present invention relates to a process of producing diamino-anthraquinonyl-oxdiazoles.

It is known (see German Patent 825,111, Example 5) to produce 2.5abis-(l.4'-diamino-2'-anthraquinonyl)- 1.3.4-oxdi-azole by reducing the nitro compound of the formula N Hz HzN O This nitro compound is prepared from l-amino-4-ni-troanthraquinone-Z-carboxylic acid chloride according to said German patent.

I have now found that, quite generally, 2-(l.4- diamino-2'-anthraquinonyl)-l.3.4-oxdiazoles can be obtained by nitration of compounds of the general formula II II N-N in which R means an organic radical, preferably a vattable radical or a group containing a vattable radical, for instance .a phenyl radical which may be substituted by vatta-ble radicals, with concentrated nitric acid, preferably such of 45 B., at temperatures up to about 100 C. and reduction in known manner. The nitro group enters the 4'-position of the anthraquinone radical upon nitrating; partial nitramine formation in 1'-position may take place at the same time. The ni-tro group and the nitramine group are converted into amino groups by the reduction. The process of the invention is essentially more simple and more convenient than that described in German Patent 825,1:111.

The 2 (l.4' diamino 2' anthraquinonyl) 1.8.4- oxdiazoles obtained according to the invention are valuable intermediates in the production of chlorine resistant blue to grey vat dyestufifs formed by acylating the 4-amino group, preferably with aromatic carboxylic acid radicals. As acylating agent, benzoyl chloride which may be substituted by halogen, alk-oxy-, alkyl-groups etc. may be used. The invention is further illustrated by the following example without being restricted thereto; the parts being by weight.

nited States Patent fifice 2,759,948 Patented Aug. 21, 1956 Example 30 parts of the most finely ground and sifted dyestuif of the formula 0 NH; NH; O I I I I t r N (-see German Patent 825,111, Example 4) are introduced While stirring and cooling with ice water into 3-30 parts of nitric acid (45 B.) which had been separated from nitrous acid by stirring with 6 parts of urea. The temperature is raised to 35-40 C. and the mixture stirred at this temperature for one hour until the red dyestuif is completely converted into colorless needles of the nitrarnino-nitro compound. After cooling the nitraminonitro compound is filtered with suction and the filtrate washed with nitric acid (specific gravity 1.4) and water. Due to the nitramino group the nitramino-nitro compound dissolves in a solution of pyridine and water with I 0 NH: NH; 0

O NHa NHz O 0 N112 NH 0 II I I f tQ-t 1%- him. Nm.

(see German Patent 825,111, Example 6). This derivative yields a chlor' e fast and water repellent marine blue vat dyestuff upon benzoylating.

In the same manner, the blue 4'-.amino derivative is produced from the red compound of the formula (prepared analogous to Example 7 of German Patent 825,111). This 4.4"-diamino compound yields a grey vat dyes-tuft upon benzoylating.

Iclaim:

l. The process for the production of 2-(1-nitrarnino- 4'-nitro-2-anthraquinonyl) 1 .3 .4-oxdiazoles which comprises nitrating 2-(1'-amino-Q-anthraquinonyl)-1.3.4-oxdiazoles with concentrated nitric acid.

2. The process which comprises ni-trating 2.'5 bis-(1'- amino-2-anthraquinonyl)-1.3.'4-oxdiazole with concentrated nitric acid to produce 2.5-bis-'(1-nitram-inonitro-2-anthraquinonyl) 1.3.4-oxdiazole.

3. The process which comprises nitrating 2-(-1'-amino- 2 anthraquinonyl) (p chlorophenyl) 1.3.4 oxdiazole with concentrated nitric acid to produce 2-(1'- nitramino 4 nitro 2' anthraquinonyl 5 (pchlorophenyl) -'1 .3 .4-oxdiazole.

4 4. The process which comprises nitrating a compound of the formula NH HQN 0 1 0 0 I II o oc o H II H H N-N N-N with concentrated nitric acid, to produce the bis-2'- nitramino-4-nitro derivative.

5. The process which comprises nitrating a compound of the formula o 2 with concentrated nitric acid, to produce the bis-2- nitrarnino-4-nitro derivative.

References Cited in the file of this patent UNITED STATES PATENTS II N 2,511,018 Stilmar June 13, 1950 2,629,718 Belshaw et al. Feb. 24, 1953 FOREIGN PATENTS 825,111 Germany Dec. 17, 1951 OTHER REFERENCES Wiley: Chem. Reviews, vol. 37, pp. 429- (1945). Bauer: Chem. Abstracts, vol. 27, p. 1628 (1933). 

1. THE PROCESS FOR THE PRODUCTION OF 2-(1''-NITRAMINO4''-NITRO-2''-ANTHRAQUINONYL)-1,3,4-OXDIAZOLES WHICH COMPRISES NITRATING 2-(1''-AMINO-2''-ANTHRAQUINONYL)-1,3,4-OXDIAZOLES WITH CONCENTRATED NITRIC ACID. 